Article with adhesive layer
阅读说明：本技术 具有粘着剂层的物品 (Article with adhesive layer ) 是由 刘淳 万启春 C·里皮善 L·T·阮 K·D·安德森 于 2018-04-27 设计创作，主要内容包括：本发明提供一种物品。所述物品包含具有两个相对表面的粘着剂层。所述粘着剂层包含(i)熔融指数为0.1g/10min至300g/10min的官能化乙烯类聚合物；(ii)0.01重量％至45重量％的官能化烃；(iii)增粘剂；及(iv)任选地,交联剂。(The invention provides an article. The article includes an adhesive layer having two opposing surfaces. The adhesive layer comprises (i) a functionalized ethylene-based polymer having a melt index of from 0.1g/10min to 300g/10 min; (ii)0.01 to 45 wt% of a functionalized hydrocarbon; (iii) a tackifier; and (iv) optionally, a crosslinking agent.)
1. An article, comprising:
an adhesive layer having two opposing surfaces, the adhesive layer comprising
(i) A functionalized ethylene-based polymer having a melt index of from 0.1g/10min to 300g/10 min;
(ii)0.01 to 45 wt% of a functionalized hydrocarbon;
(iii) a tackifier; and
(iv) a crosslinking agent.
2. The article of claim 1, further comprising a first layer in direct contact with the first surface of the adhesive layer, the first layer comprising a fabric.
3. The article of claim 2, wherein the adhesive layer is crosslinked with the first layer.
4. The article of claim 1, further comprising a second layer in direct contact with a second surface of the adhesive layer, the second layer comprising an ethylene-based polymer selected from the group consisting of: ethylene/alpha-olefin multi-block copolymers, ethylene/propylene/diene terpolymers, and combinations thereof.
5. The article of claim 4, wherein the adhesive layer is crosslinked with the second layer.
6. The article of any one of claims 1 to 5, comprising:
a first layer in direct contact with the first surface of the adhesive layer, the first layer comprising a fabric comprising fibers selected from the group consisting of: polyester fibers, polyamide fibers, cellulosic fibers, and combinations thereof; and
a second layer in direct contact with the second surface of the adhesive layer, the second layer comprising an ethylene-based polymer selected from the group consisting of: ethylene/alpha-olefin multi-block copolymers, ethylene/propylene/diene terpolymers, and combinations thereof.
7. The article of claim 6, wherein the adhesive layer is crosslinked and the article has a peel strength after initial compression of from 10g/cm to 500 g/cm.
8. The article of any one of claims 1 to 7, wherein the functionalized hydrocarbon is functionalized polybutadiene.
9. The article of any one of claims 1 to 8, wherein the functionalized hydrocarbon is maleic anhydride grafted polybutadiene.
10. The article of any one of claims 1 to 9, wherein the functionalized ethylene-based polymer is a maleic anhydride grafted ethylene-based polymer.
11. The article of any one of claims 1 to 10, wherein the adhesive layer comprises:
(i)10 to 75 weight percent of the functionalized ethylene-based polymer;
(ii) from 0.01 wt% to 45 wt% of the functionalized hydrocarbon;
(iii)5 to 55 weight percent of the tackifier; and
(iv)0.1 to 10 wt% of the crosslinker.
12. The article of any one of claims 1 to 11, wherein the adhesive layer comprises:
(i)35 to 70 weight percent maleic anhydride grafted ethylene/1-octene copolymer;
(ii) from 0.5 to 40 wt% maleic anhydride grafted polybutadiene;
(iii)10 to 50 weight percent of the tackifier; and
(iv)0.1 to 2 wt% of the crosslinker.
13. An article, comprising:
(A) an adhesive layer having two opposing surfaces, the adhesive layer comprising
(i) A functionalized ethylene-based polymer having a melt index of from 0.1g/10min to 300g/10 min;
(ii)0.01 to 45 wt% of a functionalized polybutadiene;
(iii) a tackifier;
(B) a first layer in direct contact with the first surface of the adhesive layer, the first layer comprising a fabric comprising poly (ethylene terephthalate) fibers and cotton fibers;
(C) a second layer in direct contact with the second surface of the adhesive layer, the second layer comprising an ethylene-based polymer selected from the group consisting of: ethylene/alpha-olefin multi-block copolymers, ethylene/propylene/diene terpolymers, combinations thereof;
wherein the adhesive layer is crosslinked to both the first layer and the second layer; and is
The article has a peel strength of 10g/cm to 500g/cm after initial compression.
14. The article of claim 13, wherein the peel strength of the article after final compression is 450g/cm to 6000 g/cm.
15. The article of claim 13 or 14, wherein the article is an automotive timing belt.
Technical Field
The present invention relates to an article having an adhesive layer, and further relates to an adhesive layer and a polyester fabric, and further relates to a polyester fabric adhered to a polyolefin substrate via the adhesive layer.
Background
Ethylene-based elastomers have numerous uses in timing belts (e.g., automotive timing belts), conveyor belts, textile construction, tubing, packaging films, and wire and cable applications. However, the non-polar molecular nature of ethylene-based elastomers makes them difficult to adhere, paint and/or print due to the low surface energy of conventional polyolefin adhesives.
In conventional automotive timing belt assembly processes, the adhesion between the belt layers after the initial compression process (temperature 20 ℃ to 80 ℃, pressure 0MPa to 0.5MPa, for a period of 1 to 5 seconds) must be sufficiently strong so that the individual belt layers do not separate from each other when transferred to the high temperature curing oven. In addition, the adhesion between the belt layers after the final compression process (temperature 130 ℃ to 190 ℃, pressure 0.1MPa to 1.8MPa for a period of 2 to 25 minutes) must be sufficiently strong so that the layers do not separate from each other during use of the automotive timing belt.
There is a need for an article, and in particular an automotive timing belt laminate structure, containing an adhesive layer that is capable of adhering to an ethylene-based elastomer containing layer and further for adhering an ethylene-based elastomer containing elastic layer to a fabric layer (such as a polar polymer containing fabric layer). There is a further need for an article, and in particular an automotive timing belt laminate structure, containing an adhesive layer that exhibits high peel strength after initial compression and after final compression.
Disclosure of Invention
The invention provides an article. The article includes an adhesive layer having two opposing surfaces. The adhesive layer comprises (i) a functionalized ethylene-based polymer having a melt index of from 0.1g/10min to 300g/10 min; (ii)0.01 to 45 wt% of a functionalized hydrocarbon; (iii) a tackifier; and (iv) optionally, a crosslinking agent.
Definition of
Any reference to the periodic table of elements is the periodic table of elements as published by CRC Press, inc., 1990-1991. Reference to the element groups in this table is made by the new notation of the numbered groups.
For purposes of united states patent practice, the contents of any referenced patent, patent application, or publication are incorporated by reference in their entirety (or the equivalent US version thereof is so incorporated by reference), especially with respect to the disclosure of definitions in the art (to the extent not inconsistent with any definitions specifically provided in this disclosure) and general knowledge.
The numerical ranges disclosed herein include all values from the lower and upper limit values, and include the lower and upper limit values. For ranges containing exact values (e.g., 1 or 2 or 3 to 5 or 6 or 7), any subrange between any two exact values is included (e.g., 1 to 2; 2 to 6; 5 to 7; 3 to 7; 5 to 6, etc.).
Unless stated to the contrary, implied from the context, or customary in the art, all parts and percentages are by weight and all test methods are current as of the filing date of this disclosure.
The term "composition" refers to the mixture of materials that make up the composition as well as reaction products and decomposition products formed from the materials of the composition.
The terms "comprising," "including," "having," and derivatives thereof, are not intended to exclude the presence of any additional component, step or procedure, whether or not the same is specifically disclosed. For the avoidance of any doubt, unless stated to the contrary, all compositions claimed through use of the term "comprising" may include any additional additive, adjuvant or compound, whether polymeric or otherwise. In contrast, the term "consisting essentially of … …" excludes any other components, steps, or procedures from any subsequently enumerated range, except for those that are not essential to operability. The term "consisting of … …" excludes any component, step, or procedure not specifically recited or listed. Unless stated otherwise, the term "or" means the members listed individually and in any combination. The use of the singular includes the use of the plural and vice versa.
An "anhydride" is a compound having two acyl groups bonded to the same oxygen atom.
An "acyl" group is a moiety derived by removal of a hydroxyl group from a carboxylic acid.
An "ethylene-based polymer" or "ethylene polymer" or "polyethylene" is a polymer that contains a majority amount or greater than 50 weight percent polymerized ethylene, based on the weight of the polymer, and optionally may include at least one comonomer.
An "ethylene/α -olefin interpolymer" is an interpolymer that contains a majority amount of polymerized ethylene and at least one α -olefin, based on the weight of the interpolymer.
A "fabric" is a woven or non-woven (such as knitted) structure formed from a single fiber or yarn.
"fiber" and like terms refer to elongated columns of entangled filaments.
"filament" and like terms refer to an elongated material that is a single, continuous strand having a generally circular cross-section and a length to diameter ratio of greater than 10.
A "hydrocarbon" is a compound containing only hydrogen and carbon atoms. The hydrocarbon can be (i) branched or unbranched, (ii) saturated or unsaturated, (iii) cyclic or acyclic, and (iv) any combination of (i) - (iii). Non-limiting examples of hydrocarbons include alkanes, alkenes, and alkynes.
An "interpolymer" is a polymer prepared by polymerizing at least two different types of monomers. Thus, the generic term interpolymer includes copolymers (used to refer to polymers prepared from only two different types of monomers), terpolymers (used to refer to polymers prepared from three different types of monomers), and polymers prepared from more than three different types of monomers.
"nonwoven" is a web or fabric having a structure of individual fibers or threads which are randomly embedded within one another but not in an identifiable manner as in the case of a knitted fabric.
An "olefin-based polymer" or "polyolefin" is a polymer that contains a majority amount or greater than 50 weight percent (based on the weight of the polymer) of polymerized olefin monomer (e.g., ethylene or propylene), and optionally may contain at least one comonomer. Non-limiting examples of olefin-based polymers are ethylene-based polymers.
"Polymer" is a polymeric compound prepared by polymerizing monomers of the same or different types. Thus, the generic term polymer encompasses the term "homopolymer" (used to refer to polymers prepared from only one type of monomer, with the understanding that trace amounts of impurities can be incorporated into the polymer structure) and the term "interpolymer". Trace amounts of impurities, such as catalyst residues, may be incorporated into and/or within the polymer. It also encompasses all forms of copolymers, such as random, block, and the like. The terms "ethylene/a-olefin polymer" and "propylene/a-olefin polymer" indicate copolymers prepared by polymerizing ethylene or propylene, respectively, and one or more other polymerizable a-olefin monomers, as described above. It should be noted that although polymers are often referred to as being "made from" one or more particular monomers, "based on" a particular monomer or type of monomer, "containing" a particular content of monomer, or the like, in this context, the term "monomer" should be understood to refer to the polymeric remnants of a particular monomer, and not to unpolymerized species. In general, a polymer herein refers to a "unit" based on polymerized form of the corresponding monomer.
A "timing belt" is a belt that forms part of an internal combustion engine that synchronizes rotation of the crankshaft with the camshaft so that the valves of the engine open and close at the proper times during the intake and exhaust strokes of each cylinder. A non-limiting example of a timing belt is an automotive timing belt.
"yarn" is a continuous length of twisted or entangled filaments that can be used to make woven or knitted fabrics.
Detailed Description
The invention provides an article. The article includes an adhesive layer having two opposing surfaces. The adhesive layer contains (i) a functionalized ethylene-based polymer having a melt index of 0.1g/10min to 300g/10 min; (ii)0.01 to 45 wt% of a functionalized hydrocarbon; (iii) a tackifier; and (iv) optionally, a crosslinking agent. Optionally, the article comprises a first layer in direct contact with the first surface of the adhesive layer, the first layer comprising a fabric. Optionally, the article comprises a second layer in direct contact with the second surface of the adhesive layer, the second layer comprising an ethylene-based polymer selected from the group consisting of: ethylene/alpha-olefin multi-block copolymers, ethylene/propylene/diene terpolymers, and combinations thereof.
A. Adhesive layer
The article of the present invention comprises an adhesive layer. The adhesive layer has two opposing surfaces-a first surface and a second surface. The adhesive layer contains (i) a functionalized ethylene-based polymer having a melt index of 0.1g/10min to 300g/10 min; (ii)0.01 to 45 wt% of a functionalized hydrocarbon; (iii) a tackifier; (iv) optionally, a crosslinking agent; (v) optionally, an ethylene-based polymer; (vi) optionally, a styrenic block copolymer; and (vii) optionally, an additive.
(i) Functionalized ethylene-based polymers
The adhesive layer contains a functionalized ethylene-based polymer. A "functionalized ethylene-based polymer" is an ethylene-based polymer having an acid moiety, an anhydride moiety, an amine moiety, an imide moiety, or a hydroxyl moiety bonded to the ethylene-based polymer chain (e.g., the anhydride moiety is grafted to the ethylene-based polymer chain). Non-limiting examples of suitable acids include carboxylic acids such as maleic acid, fumaric acid, itaconic acid, acrylic acid, methacrylic acid, and crotonic acid. Non-limiting examples of suitable anhydrides include carboxylic anhydrides such as maleic anhydride and itaconic anhydride. Non-limiting examples of suitable amines include primary amines, secondary amines (e.g., hydroxyethylamine), tertiary amines (e.g., trimethylamine), monoamines, diamines (e.g., 2-ethylaminoethylamine), and combinations thereof.
In one embodiment, the functionalized ethylene-based polymer is a maleic anhydride functionalized ethylene-based polymer. In another embodiment, the functionalized ethylene-based polymer is a maleic anhydride grafted ethylene-based polymer.
Functionalized ethylene-based polymerizationThe polymer is formed from a vinyl polymer. Non-limiting examples of suitable ethylene-based polymers include ethylene/a-olefin interpolymers and ethylene/a-olefin copolymers. Non-limiting examples of suitable alpha-olefins include C3-C20Alpha-olefins, or C4-C20Alpha-olefins, or C3-C10Alpha-olefins, or C4-C10Alpha-olefins, or C4-C8An alpha-olefin. Representative alpha-olefins include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, and 1-octene. In one embodiment, the functionalized ethylene-based polymer does not contain an aromatic comonomer polymerized therein. In one embodiment, the ethylene-based polymer is an ethylene/octene interpolymer.
In one embodiment, the functionalized ethylene-based polymer is a maleic anhydride functionalized ethylene/α -olefin interpolymer. In another embodiment, the functionalized ethylene/a-olefin interpolymer is or is otherwise a maleic anhydride grafted ethylene/a-olefin interpolymer ("MAH-g-ethylene/a-olefin interpolymer"). A non-limiting example of a suitable MAH-g-ethylene/α -olefin interpolymer is a MAH-g-ethylene/α -olefin copolymer (such as AMPLIFY available from The Dow Chemical Company)TMGR 216)。
In an embodiment, the functionalized ethylene-based polymer contains greater than 50 wt% of units derived from ethylene, or 51 wt%, or 55 wt%, or 60 wt% to 70 wt%, or 80 wt%, or 90 wt%, or 95 wt%, or 99 wt% of units derived from ethylene, based on the weight of the functionalized ethylene-based polymer. In one embodiment, the functionalized ethylene-based polymer contains greater than 0 wt%, or 0.01 wt%, or 0.02 wt%, or 0.03 wt%, or 0.04 wt%, or 0.05 wt%, or 0.06 wt%, or 0.07 wt%, or 0.08 wt%, or 0.09 wt%, or 0.1 wt%, or 0.2 wt%, or 0.5 wt% to 1 wt%, or 1.5 wt%, or 2 wt%, or 2.6 wt%, or 3 wt%, or 5 wt% of acid moieties, anhydride moieties, amine moieties, imide moieties, or hydroxyl moieties, based on the total weight of the functionalized ethylene-based polymer.
The functionalized ethylene-based polymer has a melt index of from 0.1g/10min to 300g/10 min. In one embodiment, the functionalized ethylene-based polymer has a melt index of 0.1g/10min, or 1g/10min to 1.5g/10min, or 2.0g/10min, or 3.0g/10min, or 5.0g/10min, or 6.0g/10min, or 8.0g/10min, or 10g/10min, or 15g/10min, or 20g/10min, or 30g/10min, or 40g/10min, or 50g/10min, or 100g/10min, or 150g/10min, or 200g/10min, or 250g/10min, or 300g/10 min.
In one embodiment, the functionalized ethylene-based polymer has a density of 0.855g/cc, or 0.860g/cc, or 0.865g/cc, or 0.870g/cc to 0.875g/cc, or 0.880g/cc, or 0.885g/cc, or 0.890g/cc, or 0.895 g/cc.
In one embodiment, the functionalized ethylene-based polymer has a melting point (Tm) of 35 ℃, or 40 ℃, or 45 ℃, or 50 ℃, or 55 ℃, or 60 ℃ to 65 ℃, or 70 ℃, or 75 ℃, or 80 ℃, or 85 ℃, or 90 ℃, or 95 ℃, or 100 ℃.
In one embodiment, the functionalized ethylene-based polymer has a glass transition temperature (Tg) of-80 deg.C, or-70 deg.C, or-60 deg.C, or-58 deg.C, or-56 deg.C to-54 deg.C, or-52 deg.C, or-50 deg.C, or-40 deg.C, or-30 deg.C, or-20 deg.C.
In an embodiment, the functionalized ethylene-based polymer or additional MAH-g-ethylene/α -olefin interpolymer has a melt index from 0.1g/10min, or from 1g/10min to 1.5g/10min, or 2.0g/10min, or 3.0g/10min, or 5.0g/10min, or 6.0g/10min, or 7.0g/10min, or 8.0g/10min, or 9.0g/10min, or 10g/10 min; and the functionalized ethylene-based polymer or the additional MAH-g-ethylene/α -olefin interpolymer has one, some, or all of the following properties: (i) at least 50 wt% units derived from ethylene; and/or (ii) greater than 0 wt%, or 0.01 wt%, or 0.02 wt%, or 0.03 wt%, or 0.04 wt%, or 0.05 wt%, or 0.06 wt%, or 0.07 wt%, or 0.08 wt%, or 0.09 wt%, or 0.1 wt%, or 0.2 wt%, or 0.5 wt% to 1 wt%, or 1.5 wt%, or 2 wt%, or 2.6 wt%, or 3 wt% of anhydride moieties; and/or (iii) a density of 0.865g/cc, or 0.870 to 0.875g/cc, or 0.880g/cc, or 0.885 g/cc; and/or (iv) a melting point (Tm) of 40 ℃, or 45 ℃, or 50 ℃, or 55 ℃, or 60 ℃ to 65 ℃, or 70 ℃; and/or (v) a glass transition temperature (Tg) of-60 ℃, or-58 ℃, or-56 ℃ to-54 ℃, or-52 ℃, or-50 ℃, or-40 ℃.
In one embodiment, the functionalized ethylene-based polymer is present in the adhesive layer in an amount of 10 wt%, or 12 wt%, or 15 wt%, or 20 wt%, or 25 wt%, or 30 wt%, or 35 wt%, or 40 wt%, or 45 wt%, or 50 wt%, or 55 wt% to 60 wt%, or 65 wt%, or 70 wt%, or 75 wt%, based on the total weight of the adhesive layer.
The adhesive layer may comprise more than one functionalized ethylene-based polymer.
The functionalized ethylene-based polymer may include two or more embodiments discussed herein.
(ii) Functionalized hydrocarbons
The adhesive layer contains a functionalized hydrocarbon. A "functionalized hydrocarbon" is a hydrocarbon polymer having an anhydride moiety bonded to a hydrocarbon polymer chain (e.g., the anhydride moiety is grafted to the hydrocarbon polymer chain). Non-limiting examples of suitable hydrocarbon polymers include polybutadiene, polyisoprene, and ethylene/propylene/diene terpolymer (EPDM) terpolymers. Non-limiting examples of suitable anhydrides include carboxylic anhydrides such as maleic anhydride and itaconic anhydride. The functionalized hydrocarbon acts as a plasticizer in the adhesive layer.
In one embodiment, the functionalized hydrocarbon is functionalized polybutadiene. The substrate polybutadiene of functionalized polybutadiene is a polymer formed from the monomer 1, 3-butadiene. In one embodiment, the matrix polybutadiene is a homopolymer containing 100 wt% units derived from 1, 3-butadiene, based on the weight of the polybutadiene. The matrix polybutadiene can be cis, trans, vinyl or a combination thereof. In one embodiment, the matrix polybutadiene is 1, 4-cis polybutadiene. In one embodiment, the functionalized polybutadiene is a maleic anhydride functionalized polybutadiene. In another embodiment, the functionalized polybutadiene is maleic anhydride grafted polybutadiene ("MAH-g-PBD"). In another embodiment, the MAH-g-PBD is maleic anhydride grafted 1, 4-cis polybutadiene. Non-limiting examples of suitable MAH-g-PBDs include POLYVEST, each available from the winning Industrial (Evonik Industries)TMMA 120 and POLYVESTTMM75。
In one embodiment, the functionalized polybutadiene contains greater than 50 wt% units derived from 1, 3-butadiene, or 51 wt%, or 55 wt%, or 60 wt%, or 65 wt% to 70 wt%, or 75 wt%, or 80 wt%, or 85 wt%, or 90 wt%, or 95 wt%, or 98 wt%, or 99 wt% units derived from 1, 3-butadiene, based on the total weight of the functionalized polybutadiene. In one embodiment, the functionalized polybutadiene contains an inverse number of anhydride moieties, or greater than 0 wt.%, or 0.01 wt.%, or 0.02 wt.%, or 0.03 wt.%, or 0.04 wt.%, or 0.05 wt.%, or 0.06 wt.%, or 0.07 wt.%, or 0.08 wt.%, or 0.09 wt.%, or 0.1 wt.%, or 0.2 wt.%, or 0.5 wt.% to 1 wt.%, or 1.5 wt.%, or 2 wt.%, or 2.6 wt.%, or 3 wt.%, or 5 wt.%, or 8 wt.%, or 10 wt.%, or 11 wt.%, or 12 wt.%, or 15 wt.% anhydride moieties, based on the total weight of the functionalized polybutadiene.
In one embodiment, the functionalized hydrocarbon has an acid number of 1mg KOH/g, or 5mg KOH/g to 10mg KOH/g, or 15mg KOH/g, or 20mg KOH/g, or 30mg KOH/g, or 40mg KOH/g, or 50mg KOH/g, or 60mg KOH/g, or 65mg KOH/g, or 70mg KOH/g to 90mg KOH/g, or 100mg KOH/g, or 110mg KOH/g, or 120mg KOH/g, or 130mg KOH/g, or 140mg KOH/g, or 150mg KOH/g.
In one embodiment, the pour point of the functionalized hydrocarbon is-40 deg.C, or-35 deg.C, or-30 deg.C, or-25 deg.C to-20 deg.C, or-15 deg.C, or-10 deg.C, or-5 deg.C, or-1 deg.C, or-0.1 deg.C, or 0 deg.C, or 5 deg.C, or 10 deg.C, or 20 deg.C.
In one embodiment, the functionalized hydrocarbon has an iodine value of 300g I2100g, or 350g I2100g, or 380g I2100g to 420g I2100g, or 450g I2100g, or 500g I2/100g。
In one embodiment, the functionalized hydrocarbon has a density of 0.90g/cc, or 0.91g/cc, or 0.92g/cc, or 0.93g/cc, or 0.94g/cc, or 0.95g/cc to 0.96g/cc, or 0.97g/cc, or 0.98g/cc, or 0.99 g/cc.
In one embodiment, the functionalized hydrocarbon has a weight average molecular weight (Mw) of 500g/mol, or 1000g/mol, or 1500g/mol, or 2000g/mol, or 2500g/mol to 3000g/mol, or 3200g/mol, or 3500g/mol, or 4000g/mol, or 5000g/mol, or 10000 g/mol.
In one embodiment, the functionalized polybutadiene or additional MAH-g-PBD or additional maleic anhydride grafted 1, 4-cis polybutadiene has one, some or all of the following properties: (i) greater than 50 weight percent of units derived from 1, 3-butadiene; and/or (ii) contains greater than 0 wt%, or 0.01 wt%, or 0.02 wt%, or 0.03 wt%, or 0.04 wt%, or 0.05 wt%, or 0.06 wt%, or 0.07 wt%, or 0.08 wt%, or 0.09 wt%, or 0.1 wt%, or 0.2 wt%, or 0.5 wt% to 1 wt%, or 1.5 wt%, or 2 wt%, or 2.6 wt%, or 3 wt%, or 5 wt%, or 8 wt%, or 10 wt%, or 11 wt%, or 12 wt%, or 15 wt% of anhydride moieties; and/or (iii) an acid number of 50mg KOH/g, or 60mg KOH/g, or 70mg KOH/g to 90mg KOH/g, or 100mg KOH/g, or 110mg KOH/g, or 120mg KOH/g, or 130mg KOH/g, or 140mg KOH/g; and/or (iv) a pour point of-30 ℃, or-25 ℃ to-20 ℃, or-15 ℃, or-10 ℃, or-5 ℃, or-1 ℃, or-0.1 ℃, or 0 ℃, or 5 ℃; and/or (v)350g I2100g, or 380g I2100g to 420g I2100g, or 450g I2Iodine number of 100 g; and/or (vi) a density of 0.94g/cc, or 0.95g/cc to 0.96g/cc, or 0.97g/cc, or 0.98 g/cc; and/or (vii) a weight average molecular weight (Mw) of 2000g/mol, or 2500g/mol to 3000g/mol, or 3200g/mol, or 3500g/mol, or 4000 g/mol.
In one embodiment, the functionalized hydrocarbon or additional functionalized polybutadiene is present in the adhesive layer in an amount of 0.01 wt%, or 0.05 wt%, or 0.1 wt%, or 0.5 wt%, or 1 wt%, or 5 wt%, or 10 wt%, or 15 wt% to 20 wt%, or 25 wt%, or 30 wt%, or 35 wt%, or 40 wt%, or 45 wt%, or 50 wt%, or 55 wt%, based on the total weight of the adhesive layer.
The functionalized hydrocarbon may include two or more of the embodiments discussed herein.
(iii) Tackifier
The adhesive layer contains a tackifier. The tackifier has a Ring and Ball softening point of 80 ℃, or 85 ℃, or 90 ℃, or 93 ℃, or 95 ℃, or 97 ℃, or 100 ℃, or 105 ℃ to 110 ℃, or 115 ℃, or 120 ℃, or 130 ℃, or 140 ℃, or 150 ℃. The tackifier may modify properties of the adhesive layer, such as viscoelastic properties (e.g., tan δ), rheological properties (e.g., viscosity), tack (e.g., tack ability), pressure sensitivity, and wetting properties. In some embodiments, the tackifier is used to improve the tack of the adhesive layer. In particular embodiments, the tackifier is used to wet through and/or improve adhesion to the adhesive surface.
Tackifiers suitable for use in the adhesive layers disclosed herein can be solid, semi-solid, or liquid at room temperature. Non-limiting examples of suitable tackifiers include (1) natural and modified rosins (e.g., gum rosin, wood rosin, high oil rosin, distilled rosin, hydrogenated rosin, dimerized rosin, and polymerized rosin); (2) glycerol and pentaerythritol esters of natural and modified rosins (e.g., glycerol ester of pale wood rosin, glycerol ester of hydrogenated rosin, glycerol ester of polymerized rosin, pentaerythritol ester of hydrogenated rosin, and phenolic modified pentaerythritol ester of rosin); (3) copolymers and terpolymers of natural terpenes (e.g., styrene/terpene and alpha methyl styrene/terpene); (4) polyterpene resins and hydrogenated polyterpene resins; (5) phenolic modified terpene resins and hydrogenated derivatives thereof (e.g., resin products resulting from the condensation of bicyclic terpenes with phenol in an acidic medium); (6) aliphatic or cycloaliphatic hydrocarbon resins and hydrogenated derivatives thereof (e.g., resins resulting from the polymerization of monomers consisting essentially of olefins and diolefins); (7) aromatic hydrocarbon resins and hydrogenated derivatives thereof; (8) aromatic modified aliphatic or cycloaliphatic hydrocarbon resins and hydrogenated derivatives thereof; and combinations thereof.
In one embodiment, the tackifier comprises aliphatic, cycloaliphatic and aromatic hydrocarbons and modified hydrocarbons and hydrogenated versions; terpenes and modified terpenes and hydrogenated forms; and rosin derivatives and hydrogenated forms; and mixtures of two or more of these tackifiers. These tackifying resins have a ring and ball softening point of 70 ℃ or from 100 ℃ to 130 ℃ or 150 ℃. It is also useful at different levels of hydrogenation or saturation (another commonly used term). Non-limiting examples of suitable tackifying resins include Eastotac from Eastman Chemical Co, Kingsport, TennTMH-100, H-115 and H-130, which are partially hydrogenated cycloaliphatic petroleum hydrocarbon resins having softening points of 100 ℃, 115 ℃ and 130 ℃, respectively. It is available as E, R, L and W grades, indicating different levels of hydrogenation, with E being the least hydrogenated and W being the most hydrogenated. Bromine number for E grade 15, bromine number for R grade 5, bromine number for L grade 3, and bromine number for W grade 1. Eastotac from Istman chemical CoTMThe softening point of H-142R was 140 ℃. Other non-limiting examples of suitable tackifying resins include EscorezTM5300. 5400 and 5637, partially hydrogenated aliphatic petroleum hydrocarbon resin, and EscorezTM5600, partially hydrogenated aromatic modified petroleum hydrocarbon resin, each available from Exxon Chemical Co, ed.h., Houston, tx; wingtackTMExtra, an aliphatic, aromatic petroleum hydrocarbon resin available from Goodyear Chemical Co., Akron, Ohio; hercoliteTM2100, partially hydrogenated cycloaliphatic petroleum hydrocarbon resin available from heoglios corporation of Wilmington, Del, tera; norsoleneTMHydrocarbon resins from Cray Valley; and ArkonTMWater white hydrogenated hydrocarbon resins, available from Arakawa Europe GmbH.
In one embodiment, the tackifier comprises an aliphatic hydrocarbon resin, such as a resin produced by polymerizing monomers consisting of olefins and diolefins (e.g., Exxon, Houston, Tex.)ESCOREZ of Mobil chemical Company (ExxonMobil chemical Company)TM1310LC、ESCOREZTM2596; or PICCOTAC from Istman chemical, Kingsport, TennTM1095、PICCOTACTM9095) And hydrogenated derivatives thereof; alicyclic petroleum hydrocarbon resins and hydrogenated derivatives thereof (e.g., ESCOREZ from Exxon Mobil chemical Co., Ltd.)TM5300 and 5400 series; EASTOTAC from Istman chemicalTMA resin). In some embodiments, the tackifier comprises a hydrogenated cyclic hydrocarbon resin (e.g., REGALREZ from Istman chemical Co., Ltd.)TMAnd REGALITETMA resin).
In one embodiment, the tackifier is free of the following groups: the anhydride-based portion of the functionalized ethylene-based polymer will react with the group.
In an embodiment, the tackifier has one, some or all of the following properties: (i) a ring and ball softening point at 80 ℃, or 85 ℃, or 90 ℃, or 93 ℃, or 95 ℃, or 97 ℃, or 100 ℃, or 105 ℃ to 110 ℃, or 115 ℃, or 120 ℃, or 130 ℃, or 140 ℃, or 150 ℃; and/or (ii) an acid number of from 0mg KOH/g to 1mg KOH/g, or 5mg KOH/g, or 10mg KOH/g, or 15mg KOH/g, or 20mg KOH/g, or 50mg KOH/g, or 100mg KOH/g, or 150mg KOH/g, or 170mg KOH/g; and/or (iii) a weight average molecular weight (Mw) of 400g/mol, or 500g/mol, or 1000g/mol to 1700g/mol, or 2000g/mol, or 2500g/mol, or 3000g/mol, or 3200g/mol, or 3500g/mol, or 4000 g/mol; and/or (iv) a number average molecular weight (Mn) of 400g/mol, or 500g/mol to 600g/mol, or 700g/mol, or 800g/mol, or 900g/mol, or 1000g/mol, or 1100 g/mol; and/or (v) a glass transition temperature (Tg) of 30 ℃, or 35 ℃, or 40 ℃ to 45 ℃, or 50 ℃, or 55 ℃. In another embodiment, the tackifier is an aliphatic hydrocarbon resin, an aliphatic and aromatic hydrocarbon resin, a polyterpene resin, a hydrogenated rosin acid, or a combination thereof.
In one embodiment, the tackifier is an aliphatic and aromatic hydrocarbon resin having a ring and ball softening point of 90 ℃, or 93 ℃, or 105 ℃ to 110 ℃, or 115 ℃, or 120 ℃, or 130 ℃, or 140 ℃.
In one embodiment, the tackifier is present in the adhesive layer in an amount of 5 wt%, or 9 wt%, or 10 wt%, or 15 wt%, or 19 wt%, or 20 wt%, or 25 wt%, or 30 wt%, or 35 wt% to 40 wt%, or 45 wt%, or 50 wt%, or 55 wt%, based on the total weight of the adhesive layer.
The tackifier may comprise two or more than two embodiments discussed herein.
(iv) Crosslinking agent
In one embodiment, the adhesive layer contains a crosslinking agent. The crosslinking agent promotes curing of the adhesive layer, and further promotes adhesion between the adhesive layer and a layer contacting the adhesive layer. A non-limiting example of a suitable crosslinking agent is a peroxide. Non-limiting examples of suitable peroxides include benzoyl peroxide, methyl ethyl ketone peroxide, t-butyl peroxide, lauroyl peroxide, and dicumyl peroxide. In one embodiment, the crosslinking agent is lauroyl peroxide, dicumyl peroxide, or a combination thereof.
In one embodiment, the crosslinking agent is present in the adhesive layer in an amount of 0.1 wt%, or 0.5 wt% to 1.0 wt%, or 1.5 wt%, or 2.0 wt%, or 3.0 wt%, or 4.0 wt%, or 5.0 wt%, or 6.0 wt%, or 7.0 wt%, or 8.0 wt%, or 9.0 wt%, or 10.0 wt%, based on the total weight of the adhesive layer.
The cross-linking agent may include two or more embodiments discussed herein.
(v) Optionally ethylenic polymers
In one embodiment, the adhesive layer contains an optional ethylene-based polymer. The optional ethylene-based polymer is different from the functionalized ethylene-based polymer in that the optional ethylene-based polymer is not functionalized (i.e., does not contain anhydride moieties).
The ethylene-based polymer can be any ethylene-based polymer disclosed herein. In one embodiment, the ethylene-based polymer is an ethylene/a-olefin interpolymer. In one embodiment, the ethylene-based polymer does not contain an aromatic comonomer polymerized therein. In one embodiment, the ethylene-based polymer is an ethylene/octene copolymer.
In an embodiment, the ethylene-based polymer is ethylene/C having one, some, or all of the following properties4-C8Alpha-olefin copolymer or another ethylene/1-octene copolymer: (i) a melt index of 0.1g/10min, or 1g/10min to 1.5g/10min, or 2.0g/10min, or 5.0g/10min, or 6.0g/10min, or 10g/10min, or 15g/10min, or 20g/10min, or 30g/10min, or 40g/10min, or 45g/10min, or 50g/10 min; and/or (ii) at least 50 wt% of units derived from ethylene; and/or (iii) a density of 0.855g/cc, or 0.859g/cc to0.865 g/cc, or 0.875g/cc, or 0.880g/cc, or 0.885g/cc, or 0.890g/cc, or 0.895 g/cc; and/or (iv) a melting point (Tm) of 35 ℃, or 40 ℃, or 45 ℃, or 50 ℃, or 55 ℃, or 60 ℃ to 65 ℃, or 70 ℃, or 75 ℃, or 80 ℃, or 85 ℃, or 90 ℃, or 95 ℃, or 100 ℃; and/or (v) a glass transition temperature (Tg) of-80 ℃, or-70 ℃, or-60 ℃, or-58 ℃, or-56 ℃ to-54 ℃, or-52 ℃, or-50 ℃, or-40 ℃, or-30 ℃, or-20 ℃.
In one embodiment, the ethylene-based polymer is present in the adhesive layer in an amount of 1.0 wt%, or 5 wt%, or 10 wt%, or 12 wt% to 25 wt%, or 30 wt%, or 35 wt%, or 37 wt%, or 40 wt%, based on the total weight of the adhesive layer.
The ethylene-based polymer may include two or more embodiments discussed herein.
(vi) Optionally styrenic block copolymers
In one embodiment, the adhesive layer contains an optional styrenic block copolymer. A "styrenic block copolymer" is an elastomer having at least one block segment of a styrenic monomer combined with another block segment of another comonomer. The styrenic block copolymer may be of the linear or radial type, or of the diblock or triblock type. Non-limiting examples of suitable styrenic block copolymers include styrene-isoprene-styrene block copolymer (SIS), styrene-butadiene-styrene block copolymer (SBS), styrene-ethylene/butylene-styrene block copolymer (SEBS), styrene-isobutylene-styrene block copolymer (SBS)Substances (SIBS), styrene-ethylene-propylene-styrene block copolymers (SEPS) and mixtures thereof. Styrenic block copolymers may be trademarked
In one embodiment, the styrenic block copolymer is functionalized. The functionalized styrenic block copolymer contains functional groups. Such functional groups are pendant grafted to the polymer chain. Functional groups can also be incorporated by copolymerizing suitable monomers containing the desired functional group. Examples of suitable functional groups include halo groups (especially chloro and bromo groups), hydroxyl groups, carboxyl groups, carbonyl groups, phosphonyl groups, anhydride groups, amino groups, epoxy groups, mercapto groups, sulfate groups, sulfonate groups, amide groups, and ester groups. Non-limiting examples of unsaturated carboxylic acid and anhydride compounds that can be grafted onto the preformed styrenic block copolymer include maleic acid, fumaric acid, itaconic acid, acrylic acid, methacrylic acid, crotonic acid, maleic anhydride, and itaconic anhydride. In one embodiment, the functionalized styrenic block copolymer is a maleic anhydride functionalized styrenic block copolymer.
In one embodiment, the styrenic block copolymer is present in the adhesive layer in an amount of 1.0 wt%, or 5 wt%, or 10 wt%, or 12 wt% to 25 wt%, or 30 wt%, or 35 wt%, or 37 wt%, or 40 wt%, based on the total weight of the adhesive layer.
Styrenic block copolymers may include both of the more embodiments disclosed herein.
(vii) Optional additives
In one embodiment, the adhesive layer contains optional additives. Non-limiting examples of suitable additives include plasticizers, oils, stabilizers, antioxidants, pigments, dyes, anti-caking additives, polymeric additives, defoamers, preservatives, thickeners, rheology modifiers, humectants, fillers, solvents, nucleating agents, surfactants, chelating agents, gelling agents, processing aids, neutralizers, flame retardants, fluorescers, compatibilizers, biocides, water, and combinations thereof.
In one embodiment, the additive is present in the adhesive layer in an amount of 0.1 wt%, or 0.2 wt%, or 0.3 wt%, or 0.4 wt% to 0.5 wt%, or 0.6 wt%, or 0.7 wt%, or 0.8 wt%, or 1.0 wt%, or 2.0 wt%, or 2.5 wt%, or 3.0 wt%, based on the total weight of the adhesive layer.
The additives may include both of the further embodiments disclosed herein.
In one embodiment, the adhesive layer is applied to another layer (such as the first layer or the second layer) as part of an adhesive composition. The adhesive composition contains (i) a functionalized ethylene-based polymer having a melt index of 0.1g/10min to 300g/10 min; (ii)0.01 to 45 wt% of a functionalized hydrocarbon (e.g., functionalized polybutadiene); (iii) a tackifier; (iv) optionally, a crosslinking agent; (v) optionally, an ethylene-based polymer; (vi) optionally, a styrenic block copolymer; (vii) optionally, an additive; and (viii) a solvent.
(viii) Solvent-based adhesive composition
In one embodiment, an adhesive composition is provided. The adhesive composition includes a solvent. The solvent may be a hydrocarbon solvent, a polar solvent, and combinations thereof.
In one embodiment, the solvent is a hydrocarbon solvent. In one embodiment, the hydrocarbon solvent is selected from the group consisting of aromatic hydrocarbon solvents, aliphatic hydrocarbon solvents, and combinations thereof. An "aromatic hydrocarbon" is a hydrocarbon containing one or more benzene rings. Non-limiting examples of aromatic hydrocarbon solvents include toluene and xylene. An "aliphatic hydrocarbon" is a hydrocarbon that is an alkane, alkene, alkyne, or a derivative of an alkane, alkene, or alkyne. Aliphatic hydrocarbons do not include aromatic hydrocarbons. Non-limiting examples of aliphatic hydrocarbon solvents include hexane, cyclohexane, and methylcyclohexane.
In one embodiment, the solvent is a polar solvent. A "polar solvent" is a solvent containing polar groups. A "polar group" is any group that imparts a bond dipole moment to an otherwise substantially non-polar molecule. Exemplary polar groups include alcohols, carboxyl groups, and carboxylic acid esters. Non-limiting examples of polar solvents include alcohols, ketones, esters, and water. Non-limiting examples of suitable ketones include acetone, methyl ethyl ketone, and cyclohexanone. Non-limiting examples of suitable esters include butyl acetate and ethyl acetate.
In one embodiment, the solvent is methylcyclohexane, cyclohexanone, toluene, methyl ethyl ketone, or a combination thereof.
The solvent may comprise two or more embodiments disclosed herein.
In one embodiment, the adhesive composition is formed by mixing under heat: (i) a functionalized ethylene-based polymer having a melt index of from 0.1g/10min to 300g/10 min; (ii)0.01 wt% to 45 wt% functionalized hydrocarbon; (iii) a tackifier; (iv) optionally, a crosslinking agent; (v) optionally, an ethylene-based polymer; (vi) optionally, a styrenic block copolymer; (vii) optionally, an additive; and (viii) a solvent to dissolve or partially dissolve components (i) - (vii) in the solvent.
In one embodiment, an adhesive layer of the invention is applied to another layer (such as a first layer or a second layer) as part of an adhesive composition. Non-limiting examples of suitable methods to apply the adhesive composition to the first layer or the second layer include casting, rod coating, roll coating, brushing, dipping, pouring, or spraying techniques.
After the adhesive composition is applied to the first layer or the second layer, it is dried to evaporate at least 90 wt% or 98 wt% or 99 wt% or 100 wt% of the solvent based on the weight of the solvent in the adhesive composition to form the adhesive layer. In one embodiment, 100 wt% of the solvent is evaporated, based on the weight of the total weight of solvents in the adhesive composition. Non-limiting examples of methods to dry the adhesive composition include drying the article in an oven at a temperature equal to or greater than 80 ℃ for at least 0.5 minutes, at least 1 minute, at least 2 minutes, or at least 3 minutes, or at least 4 minutes, or at least 5 minutes.
In one embodiment, the coating weight of the adhesive layer after drying is 50g/m2Or 60g/m2Or 70g/m2Or 80g/m2Or 85g/m2Or 90g/m2To 100g/m2Or 110g/m2Or 120g/m2Or 130g/m2Or 140g/m2Or 150g/m2Or 160g/m2Or 170g/m2。
In one embodiment, the adhesive layer comprises, based on the total weight of the adhesive layer: (i)10 wt%, or 12 wt%, or 15 wt%, or 20 wt%, or 25 wt%, or 30 wt%, or 35 wt%, or 40 wt%, or 45 wt%, or 50 wt%, or 55 wt% to 60 wt%, or 65 wt%, or 70 wt%, or 75 wt% of a functionalized ethylene-based polymer having a melt index of 0.1g/10min to 50g/10min, or 300g/10 min; (ii)0.01 wt%, or 0.05 wt%, or 0.5 wt%, or 1 wt%, or 5 wt%, or 10 wt%, or 15 wt% to 20 wt%, or 25 wt%, or 30 wt%, or 35 wt%, or 40 wt%, or 45 wt% of a functionalized hydrocarbon (e.g., functionalized polybutadiene); (iii)5 wt%, or 9 wt%, or 10 wt%, or 15 wt%, or 20 wt%, or 25 wt%, or 30 wt%, or 35 wt% to 40 wt%, or 45 wt%, or 50 wt%, or 55 wt% tackifier; (iv) optionally, 0 wt%, or 0.1 wt%, or 0.5 wt% to 1.0 wt%, or 1.5 wt%, or 2.0 wt%, or 3.0 wt%, or 4.0 wt%, or 5.0 wt%, or 6.0 wt%, or 7.0 wt%, or 8.0 wt%, or 9.0 wt%, or 10.0 wt% of a crosslinking agent; (v) optionally, 0 wt%, or 1.0 wt%, or 5 wt%, or 10 wt%, or 12 wt% to 25 wt%, or 30 wt%, or 35 wt%, or 37 wt%, or 40 wt% of an ethylene-based polymer; (vi) optionally, 0 wt%, or 1.0 wt%, or 5 wt%, or 10 wt%, or 12 wt% to 25 wt%, or 30 wt%, or 35 wt%, or 37 wt%, or 40 wt% of a styrenic block copolymer; and (vii) optionally, 0 wt%, or 0.1 wt%, or 0.2 wt%, or 0.3 wt%, or 0.4 wt% to 0.5 wt%, or 0.6 wt%, or 0.7 wt%, or 0.8 wt%, or 1.0 wt%, or 2.0 wt%, or 2.5 wt%, or 3.0 wt% of an additive.
The adhesive layer and adhesive composition may include two or more embodiments disclosed herein.
B. First layer
In one embodiment, the article of the present invention comprises a first layer in direct contact with the first surface of the adhesive layer. The first layer comprises a fabric. In one embodiment, the fabric is formed from a single fiber or yarn that is polyester, polyamide (such as nylon), cellulose, fiberglass, para-aramid, or a combination thereof. A non-limiting example of a suitable polyester is polyethylene terephthalate (PET). A non-limiting example of a suitable cellulose is cotton. In one embodiment, the fabric comprises PET fibers and cotton fibers. In one embodiment, 50 wt%, or 51 wt%, or 75 wt% to 90 wt%, 100 wt% of the textile fibers and/or textile yarns are polyester, polyamide, cellulose, fiberglass, para-aramid, or combinations thereof.
The fabric may be woven or non-woven (such as knitted). In one embodiment, the fabric is a knit fabric. "knit" is a wound yarn or fiber in a series of connected loops, formed manually with knitting needles or with a machine. The fabric may be formed by warp or weft knitting, flat knitting and circular knitting. Non-limiting examples of suitable warp knit fabrics include tricot, raschel stretch fabrics (raschel powernet), and lacing. Non-limiting examples of suitable weft knit fabrics include circular, flat, and seamless (often viewed as a subset of circular knit fabrics).
In an embodiment, the thickness of the fabric is 20 μm, or 50 μm, or 100 μm, or 200 μm, or 300 μm, or 400 μm to 500 μm, or 900 μm, or 1000 μm, or 1500 μm, or 2000 μm, or 3000 μm.
The first layer and further the fabric may comprise two or more embodiments disclosed herein.
C. Second layer
In one embodiment, the article of the present invention comprises a second layer in direct contact with the second surface of the adhesive layer. The second layer comprises an ethylene-based polymer selected from the group consisting of: (1) ethylene/alpha-olefin multi-block copolymers, (2) ethylene/propylene/diene terpolymers, and combinations thereof. In one embodiment, the second layer comprises (3) an optional additive.
(1) Ethylene/alpha-olefin multi-block copolymers
In one embodiment, the second layer comprises an ethylene/a-olefin multi-block copolymer. The term "ethylene/α -olefin multiblock copolymer" refers to an ethylene/C4-C8 α -olefin multiblock copolymer composed of ethylene and one copolymerizable C4-C8 α -olefin comonomer in polymerized form, said polymer being characterized by multiple blocks or segments of two polymerized monomer units differing in chemical or physical properties, said blocks being joined (or covalently bonded) in a linear manner, i.e., a polymer comprising chemically distinct units joined end-to-end relative to polymerized ethylenic functionality. Ethylene/a-olefin multi-block copolymers include block copolymers having two blocks (diblock) and more than two blocks (multiblock). The C4-C8 alpha-olefin is selected from butene, hexene and octene. The ethylene/a-olefin multi-block copolymer has no or otherwise excludes styrene (i.e., no styrene) and/or vinyl aromatic monomers and/or conjugated dienes. When referring to the amount of "ethylene" or "comonomer" in a copolymer, it is understood that this refers to the polymerized units thereof. In some embodiments, the ethylene/a-olefin multi-block copolymer may be represented by the formula: (AB) n; wherein n is an integer of at least 1, preferably greater than 1, such as 2, 3, 4,5, 10, 15, 20, 30, 40, 50, 60, 70, 80, 90, 100 or greater than 100, "a" represents a hard block or segment and "B" represents a soft block or segment. A and B are linked or covalently bonded in a substantially linear fashion or in a linear fashion as opposed to a substantially branched or substantially star-shaped fashion. In other embodiments, the a and B blocks are randomly distributed along the polymer chain. In other words, block copolymers generally do not have the following structure: AAA-AA-BBB-BB. In one embodiment, the ethylene/a-olefin multi-block copolymer does not have a third type of block comprising a different comonomer. In another embodiment, each of block a and block B has monomers or comonomers substantially randomly distributed within the block. In other words, neither block a nor block B includes two or more sub-segments (or sub-blocks) having a unique composition, such as end segments, whose composition is substantially different from the remainder of the block.
Preferably, ethylene comprises the majority mole fraction of the overall ethylene/a-olefin multi-block copolymer, i.e., ethylene comprises at least 50 mole percent of the overall ethylene/a-olefin multi-block copolymer. More preferably, the ethylene comprises at least 60 mole percent, at least 70 mole percent, or at least 80 mole percent, with the substantial remainder of the overall ethylene/a-olefin multi-block copolymer comprising C4-C8An alpha-olefin comonomer. In an embodiment, the ethylene/α -olefin multi-block copolymer contains 50 to 90 mole% ethylene, or 60 to 85 mole% ethylene, or 65 to 80 mole% ethylene. For many ethylene/octene multi-block copolymers, the composition includes an ethylene content greater than 80 mole percent of the overall ethylene/octene multi-block copolymer and an octene content of 10 to 15 mole percent, or 15 to 20 mole percent, of the overall multi-block copolymer.
Ethylene/a-olefin multi-block copolymers contain varying amounts of "hard" and "soft" segments. A "hard" segment is a block of polymerized units in which ethylene is present in an amount greater than 90 wt%, or 95 wt%, or greater than 98 wt%, up to 100 wt%, based on the weight of the polymer. In other words, the comonomer content (content of monomers other than ethylene) in the hard segments is less than 10 wt% or 5 wt%, or less than 2 wt% based on the weight of the polymer, and can be as low as zero. In some embodiments, the hard segments comprise all or substantially all units derived from ethylene. "soft" segments are blocks of polymerized units having a comonomer content (the content of monomers other than ethylene) of greater than 5 wt.%, or greater than 8 wt.%, greater than 10 wt.%, or greater than 15 wt.%, based on the weight of the polymer. In an embodiment, the comonomer content in the soft segment is greater than 20 wt.%, greater than 25 wt.%, greater than 30 wt.%, greater than 35 wt.%, greater than 40 wt.%, greater than 45 wt.%, greater than 50 wt.%, or greater than 60 wt.%, and can be up to 100 wt.%.
The soft segment can be present in the ethylene/a-olefin multiblock copolymer from 1 wt% to 99 wt%, or from 5 wt% to 95 wt%, from 10 wt% to 90 wt%, from 15 wt% to 85 wt%, from 20 wt% to 80 wt%, from 25 wt% to 75 wt%, from 30 wt% to 70 wt%, from 35 wt% to 65 wt%, from 40 wt% to 60 wt%, or from 45 wt% to 55 wt% of the total weight of the ethylene/a-olefin multiblock copolymer. Conversely, hard segments may be present in similar ranges. The soft segment weight percent and hard segment weight percent can be calculated based on data obtained from DSC or NMR. Such methods and calculations are disclosed, for example, in USP 7,608,668 entitled "Ethylene/α -Olefin Block interpolymer" in the name of Colin l.p.shann, Lonnie hazlit et al, filed on 3/15 d 2006 and assigned to Dow Global technology inc, the disclosure of which is incorporated herein by reference in its entirety. Specifically, the weight percent of hard and soft segments and the comonomer content can be determined as described in column 57 to column 63 of USP 7,608,668.
Ethylene/α -olefin multi-block copolymers comprise two or more chemically distinct regions or segments (referred to as "blocks") joined (or covalently bonded) in a linear fashion, i.e., they contain chemically distinct units joined end-to-end, rather than in a pendant or grafted fashion, relative to the polymeric ethylenic functionality. In one embodiment, the blocks differ in the following respects: the amount or type of comonomer incorporated, density, crystallinity, crystallite size attributable to polymers of such composition, type or degree of stereoisomerism (isotactic or syndiotactic), regioregularity or regioirregularity, amount of branching (including long chain branching or hyper-branching), homogeneity or any other chemical or physical property. Compared to prior art block interpolymers comprising interpolymers made by continuous monomer addition, rheological catalysts, or anionic polymerization techniques, the ethylene/α -olefin multiblock copolymers of the present invention are characterized by a unique distribution of polymer polydispersity (PDI or Mw/Mn or MWD), polydisperse block length distribution, and/or polydisperse block number distribution throughout, which in one embodiment is due to the effect of a shuttling agent in combination with the various catalysts used in their preparation.
In an embodiment, the ethylene/a-olefin multi-block copolymer is made in a continuous process and has a polydispersity index (Mw/Mn) of 1.7 to 3.5, or 1.8 to 3, or 1.8 to 2.5, or 1.8 to 2.2. When made in a batch or semi-batch process, the ethylene/α -olefin multi-block copolymer has a Mw/Mn of 1.0 to 3.5, or 1.3 to 3, or 1.4 to 2.5, or 1.4 to 2.
In addition, the ethylene/α -olefin multi-block copolymer has a PDI (or Mw/Mn) that fits a Schultz-Flory distribution rather than a Poisson distribution. The ethylene/alpha-olefin multi-block copolymer of the present invention has both a polydisperse block distribution as well as a polydisperse block size distribution. This results in the formation of polymer products with improved and distinguishable physical properties. The theoretical benefits of polydisperse block distributions have been modeled and discussed previously in Potemkin, physical Review E (1998)57(6), pages 6902-6912 and Dobrynin, journal of chemi-physical (J.chem.Phyvs.) 107(21), pages 9234-9238.
In one embodiment, the ethylene/α -olefin multi-block copolymer of the present invention has the largest possible distribution of block lengths.
In another embodiment, the ethylene/α -olefin multi-block copolymers of the present invention, especially copolymers made in a continuous solution polymerization reactor, have the largest possible distribution of block lengths. In one embodiment of the present invention, an ethylene/α -olefin multi-block copolymer is defined as having:
(A) a Mw/Mn from about 1.7 to about 3.5, at least one melting point, Tm, in degrees Celsius, and a density, d, in grams/cubic centimeter, wherein the numerical values of Tm and d correspond to the relationship:
Tm>-2002.9+4538.5(d)-2422.2(d)2and/or
(B) An Mw/Mn from about 1.7 to about 3.5, and is characterized by a heat of fusion, Δ H, in J/g, and a difference, Δ T, in degrees Celsius defined as the temperature difference between the tallest DSC peak and the tallest crystallization analytical fractionation ("CRYSTAF") peak, wherein the numerical values of Δ T and Δ H have the following relationships:
for Δ H greater than zero and up to 130J/g, Δ T > -0.1299 Δ H +62.81
For a Δ H greater than 130J/g, a Δ T of 48 ℃ or higher
Wherein the CRYSTAF peak is determined using at least 5 percent cumulative polymer, and if less than 5 percent of the polymer has an identifiable CRYSTAF peak, then the CRYSTAF temperature is 30 ℃; and/or
(C) An elastic recovery, Re, in percent measured at 300% strain and 1 cycle with a compression molded ethylene/α -olefin interpolymer film and having a density, d, in grams/cubic centimeter, wherein the numerical values of Re and d satisfy the following relationship when the ethylene/α -olefin interpolymer is substantially free of a crosslinked phase:
re >1481-1629 (d); and/or
(D) Having a molecular fraction eluted between 40 ℃ and 130 ℃ when fractionated using TREF, characterized in that the fraction eluted is at least 5% higher in molar comonomer content than a comparable random ethylene interpolymer eluted between the same temperatures, wherein the comparable random ethylene interpolymer has the same comonomer and has a melt index, density, and molar comonomer content (based on the entire polymer) within 10% of the ethylene/a-olefin interpolymer; and/or
(E) Has a storage modulus G '(25 ℃) at 25 ℃ and a storage modulus G' (100 ℃) at 100 ℃, wherein the ratio of G '(25 ℃) to G' (100 ℃) is in the range of 1:1 to 9: 1.
The ethylene/α -olefin multi-block copolymer may also have:
(F) a fraction of molecules eluting between 40 ℃ and 130 ℃ when fractionated using TREF, characterized in that the fraction has a block index of at least 0.5 and at most 1 and a molecular weight distribution Mw/Mn of greater than 1.3; and/or
(G) An average block index greater than zero and up to 1.0 and a molecular weight distribution Mw/Mn greater than 1.3.
It is to be understood that the ethylene/a-olefin multi-block copolymer can have one, some, all, or any combination of properties (a) - (G). The block index can be determined as described in detail in USP 7,608,668 (which is incorporated herein by reference for that purpose). Analytical methods for determining properties (a) to (G) are disclosed, for example, in USP 7,608,668, column 31, line 26 to column 35, line 44, which are incorporated herein by reference for that purpose.
In one embodiment, the ethylene/α -olefin multi-block copolymer has hard segments and soft segments, is free of styrene, and consists of only (i) ethylene and (ii) C4-C8An alpha-olefin composition and is defined as having a Mw/Mn from 1.7 to 3.5, at least one melting point, Tm, in degrees Celsius, and a density, d, in grams/cubic centimeter, wherein the numerical values of Tm and d correspond to the relationship:
Tm>-2002.9+4538.5(d)-2422.2(d)2，
wherein the density d is 0.850g/cc, or 0.860g/cc, or 0.870g/cc, or 0.875g/cc to 0.880g/cc, or 0.890 g/cc; and a melting point Tm of 110 ℃, or 115 ℃, or 120 ℃ to 125 ℃, or 130 ℃, or 135 ℃.
In one embodiment, the ethylene/a-olefin multi-block copolymer is an ethylene/1-octene multi-block copolymer (consisting only of ethylene and octene comonomers) and has one, some, or all of the following properties: (1) an Mw/Mn of 1.7, or 1.8 to 2.2, or 2.5, or 3.5; and/or (2) a density of 0.860g/cc, or 0.865g/cc to 0.870g/cc, or 0.880 g/cc; and/or (3) a melting point Tm of 110 ℃, or 115 ℃ to 125 ℃, or 130 ℃, or 135 ℃; and/or (4) a Melt Index (MI) of 0.1g/10min, or 0.5g/10min to 1.0g/10min, or 2.0g/10min, or 5g/10min, or 10g/10 min; and/or (5)50 to 85 wt% soft segment and 40 to 15 wt% hard segment; and/or (6)10 mol%, or 13 mol%%, or 14 mol%, or 15 mol% to 16 mol%, or 17 mol%, or 18 mol%, or 19 mol%, or 20 mol% C4-C12An alpha-olefin in the soft segment; and/or (7)0.5 mole%, or 1.0 mole%, or 2.0 mole%, or 3.0 mole% to 4.0 mole%, or 5 mole%, or 6 mole%, or 7 mole%, or 9 mole% octenes in the hard segments; and/or (8) at 300% 300% min as measured according to ASTM D1708·1Elastic recovery (Re) at 21 ℃ of 50%, or 60% to 70%, or 80%, or 90% at deformation; and/or (9) polydisperse block distribution and polydisperse block size distribution.
In one embodiment, the ethylene/α -olefin multi-block copolymer is an ethylene/octene multi-block copolymer. In one embodiment, the ethylene/octene multi-block copolymer is under the trade name INFUSETMSold by the Dow chemical company of Midland, Michigan, USA, Mich.
The ethylene/a-olefin multi-block copolymer can be made via a chain shuttling process such as described in USP 7,858,706, which is incorporated herein by reference. Specifically, suitable chain shuttling agents and related information are listed in column 16, line 39 through column 19, line 44. Suitable catalysts are described in column 19, line 45 to column 46, line 19 and suitable cocatalysts are described in column 46, line 20 to column 51, line 28. The methods are described throughout the literature, but in particular in column 51, line 29 to column 54, line 56. The method is also described, for example, in the following: USP 7,608,668; USP 7,893,166; and USP 7,947,793.
The second layer may comprise more than one ethylene/a-olefin multi-block copolymer.
In an embodiment, the second layer contains 10 wt%, or 20 wt%, or 25 wt%, or 30 wt% to 35 wt%, or 40 wt%, or 45 wt%, or 50 wt%, or 60 wt%, or 70 wt%, or 80 wt%, or 90 wt%, or 100 wt% of the ethylene/a-olefin multi-block copolymer, based on the total weight of the second layer.
The ethylene/a-olefin multi-block copolymer may include two or more embodiments disclosed herein.
(2) Ethylene/propylene/diene terpolymers
In one embodiment, the second layer comprises an ethylene/propylene/diene terpolymer. An "ethylene/propylene/diene terpolymer" ("EPDM") is a polymer having a majority weight percent (i.e., greater than 50 weight percent) of units derived from ethylene, and also includes units derived from a propylene comonomer and units derived from a diene comonomer.
EPDM terpolymers contain units derived from diene monomers. The diene may be a conjugated, non-conjugated, straight chain, branched chain or cyclic hydrocarbon diene having from 6 to 15 carbon atoms. Non-limiting examples of suitable dienes include 1, 4-hexadiene; 1, 6-octadiene; 1, 7-octadiene; 1, 9-decadiene; branched non-cyclic dienes such as 5-methyl-1, 4-hexadiene, 3, 7-dimethyl-1, 6-octadiene, 3, 7-dimethyl-1, 7-octadiene, and mixed isomers of dihydromyrcene and dihydroocimene; monocyclic alicyclic dienes such as 1, 3-cyclopentadiene, 1, 4-cyclohexadiene, 1, 5-cyclooctadiene and 1, 5-cyclododecadiene; and polycyclic alicyclic fused and bridged cyclic dienes such as tetrahydroindene, methyltetrahydroindene, dicyclopentadiene, and bicyclo- (2,2,1) -hepta-2, 5-diene; alkenyl, alkylene, cycloalkenyl and cycloalkylidene norbornenes such as 5-methylene-2-norbornene (MNB), 5-propenyl-2-norbornene, 5-isopropylidene-2-norbornene, 5- (4-cyclopentenyl) -2-norbornene, 5-cyclohexylidene-2-norbornene, 5-vinyl-2-norbornene, norbornadiene, 5-ethylidene-2-norbornene (ENB), 5-vinylidene-2-norbornene (VNB), 5-methylene-2-norbornene (MNB), dicyclopentadiene (DCPD); and combinations thereof. Other non-limiting examples of suitable dienes include 4-methyl-1, 4-hexadiene, 7-methyl-1, 6-octadiene, 5, 7-dimethyl-1, 6-octadiene, 3,7, 11-trimethyl-1, 6, 10-octatriene, 6-methyl-1, 5-heptadiene, 1, 3-butadiene, 1, 6-heptadiene, 1, 8-nonadiene, 1, 9-decadiene, 1, 10-undecadiene, 1, 5-cyclododecadiene, bicyclo [2.2.1]Hepta-2, 5-diene (norbornadiene), tetracyclododecene, butadiene, dicyclopentadiene, vinylnorbornene, mixed isomers of dihydromyrcene and dihydroocimene, tetrahydroindene, methylTetrahydroindene, 5-propenyl-2-norbornene, 5-isopropylidene-2-norbornene, 5- (4-cyclopentenyl) -2-norbornene, 5-cyclohexylidene-2-norbornene, 5-vinyl-2-norbornene, and combinations thereof. A non-limiting example of a suitable EPDM terpolymer is NORDEL available from the Dow chemical companyTMIP 3760P。
The second layer may comprise more than one EPDM terpolymer.
In an embodiment, the second layer contains 20 wt%, or 25 wt%, or 30 wt% to 35 wt%, or 40 wt%, or 45 wt%, or 50 wt%, or 60 wt%, or 70 wt%, or 80 wt%, or 90 wt% EPDM terpolymer based on the total weight of the second layer.
EPDM terpolymers can include two or more than two embodiments disclosed herein.
(3) Optional additives
In one embodiment, the second layer comprises optional additives. Non-limiting examples of suitable additives include fillers (e.g., carbon black and silica), plasticizers, oils (e.g., paraffin oil), stabilizers, antioxidants (e.g., zinc 2-mercaptotoluyleneindazole, 4' -bis (alpha, alpha-dimethylbenzyl) diphenylamine, and polymeric 1, 2-dihydro-2, 2, 4-trimethylquinoline), pigments, dyes, antiblock additives, polymeric additives, defoamers, preservatives, thickeners, rheology modifiers, humectants, fillers, solvents, nucleating agents, surfactants, chelating agents, gelling agents, processing aids, neutralizing agents, flame retardants, fluorescing agents, compatibilizers, antimicrobial agents, adjuvants (e.g., trimethylolpropane trimethacrylate (TMPTMA)), crosslinking agents (e.g., dicumyl peroxide), water, and combinations thereof.
In one embodiment, the second layer comprises, based on the total weight of the second layer: (1)0 wt%, or 30 wt%, or 35 wt%, or 40 wt%, or 45 wt% to 50 wt%, or 55 wt%, or 60 wt% of an ethylene/a-olefin multi-block copolymer; (2)0 wt%, or 20 wt%, or 25 wt%, or 30 wt% to 35 wt%, or 40 wt%, or 45 wt%, or 50 wt% EPDM terpolymer; (3)0 wt%, or 30 wt%, or 40 wt%, or 45 wt% to 50 wt%, or 55 wt%, or 60 wt%, or 65 wt%, or 70 wt%, or 75 wt%, or 80 wt% filler; (4)0 wt%, or 5 wt%, or 6 wt% to 10 wt%, or 15 wt%, or 20 wt%, or 25 wt% oil; (5)0 wt%, or 0.1 wt%, or 0.5 wt%, or 1.0 wt%, or 2.0 wt% to 2.3 wt%, or 2.5 wt%, or 3.0 wt% crosslinker; (6)0 wt%, or 0.1 wt%, or 0.5 wt%, or 1.0 wt%, or 1.2 wt% to 1.4 wt%, or 1.5 wt%, or 2.0 wt% adjuvant; and (7)0 wt%, or 0.1 wt%, or 0.5 wt%, or 1.0 wt%, or 1.5 wt% to 2.0 wt%, or 2.5 wt%, or 3.0 wt% antioxidant.
The second layer may comprise two or more embodiments disclosed herein.
It is understood that the sum of the components in each of the compositions and layers disclosed herein, including the aforementioned layers, yields 100 weight percent (wt%).
D. Article with a cover
The invention provides an article. In one embodiment, an article comprises: (A) an adhesive layer having two opposing surfaces; (B) optionally, a first layer in direct contact with the first surface of the adhesive layer, the first layer comprising a fabric; and (C) optionally, a second layer in direct contact with the second surface of the adhesive layer, the second layer comprising an ethylene-based polymer selected from the group consisting of: ethylene/alpha-olefin multi-block copolymers, EPDM terpolymers, and combinations thereof. In one embodiment, the adhesive layer is crosslinked with the first layer and/or the second layer.
In one embodiment, an adhesive layer is applied to the first layer as part of an adhesive composition and then dried to form an adhesive layer of the article having the following structure: first layer/adhesive layer.
In one embodiment, a second layer is applied to the second surface of the adhesive layer. In one embodiment, a second layer is applied to the second surface of the adhesive layer to form a laminate article having the structure: first layer/adhesive layer/second layer (hereinafter "structure 1").
In an embodiment, the structure is subsequently compressed at a temperature of 20 ℃, or 30 ℃, or 40 ℃, or 50 ℃, or 60 ℃ to 70 ℃, or 80 ℃ and a pressure of 0MPa, or 0.1MPa, or 0.2MPa to 0.3MPa, or 0.4MPa, or 0.5MPa for a period of 11 seconds to 2 seconds, or 5 seconds (hereinafter "initial compression"). The initial compression is performed via roll processing. After initial compression, at least a portion of the adhesive layer is crosslinked with the first layer and/or the second layer. In an embodiment, the peel strength of the article after the initial compression is 10g/cm, or 20g/cm, or 30g/cm, or 40g/cm, or 50g/cm, or 60g/cm, or 70g/cm, or 80g/cm, or 90g/cm, or 100g/cm, or 110g/cm, or 120g/cm, or 130g/cm, or 140g/cm to 150g/cm, or 160g/cm, or 170g/cm, or 180g/cm, or 190g/cm, or 200g/cm, or 300g/cm, or 400g/cm, or 500 g/cm. The higher peel strength after initial compression is advantageous because it prevents the layers of the article from separating from each other during transfer to the high temperature curing oven.
In an embodiment, after structure 1 undergoes initial compression, it is compressed at a temperature of 130 ℃, or 140 ℃, or 150 ℃, or 160 ℃, or 170 ℃ to 180 ℃, or 190 ℃ and a pressure of 0.1MPa, or 0.5MPa, or 0.6MPa to 0.7MPa, or 0.8MPa, or 1.0MPa, or 1.5MPa, or 1.8MPa, for a period of 2 minutes, or 5 minutes, or 10 minutes to 15 minutes, or 20 minutes, or 25 minutes (hereinafter "final compression"). In one embodiment, the final compression is performed using a compression molder. In one embodiment, at least a portion of the adhesive layer is crosslinked with the first layer and/or the second layer after final compression. In an embodiment, the peel strength of the article after final compression is 450g/cm, or 500g/cm, or 750g/cm, or 1000g/cm, or 1100g/cm, or 1200g/cm, or 1300g/cm, or 1400g/cm, or 1500g/cm, or 1600g/cm, or 1700g/cm, or 1800g/cm, or 1900g/cm, or 2000g/cm, or 2500g/cm, or 3000g/cm, or 3500g/cm to 4000g/cm, or 5000g/cm, or 5500g/cm, or 6000 g/cm. A higher peel strength after final compression is advantageous because it prevents the layers of the article from separating from each other during use of the article.
Non-limiting examples of suitable articles include timing belts (e.g., automotive timing belts); a conveyor belt; coating the fabric; textile structures such as banners and tents; reinforcing the pipeline; a multilayer encapsulation film; and wire and cable applications. In one embodiment, the article is a timing belt.
In one embodiment, the article is an automotive timing belt. In one embodiment, an article comprises: (A) an adhesive layer having two opposing surfaces, the adhesive layer comprising (i) a functionalized ethylene-based polymer having a melt index of from 0.1g/10min to 300g/10 min; (ii)0.01 to 45 wt% of a functionalized hydrocarbon (e.g., functionalized polybutadiene); (iii) a tackifier; (iv) optionally, a crosslinking agent; (v) optionally, an ethylene-based polymer; (vi) optionally, a styrenic block copolymer; and (vii) optionally, an additive; (B) a first layer in direct contact with the first surface of the adhesive layer, the first layer comprising a fabric (e.g., a fabric having PET fibers and cotton fibers); (C) a second layer in direct contact with the second surface of the adhesive layer, the second layer comprising an ethylene-based polymer selected from the group consisting of: (1) ethylene/alpha-olefin multi-block copolymers, (2) ethylene/propylene/diene terpolymers, and combinations thereof; and optionally additives; and the article has one, some or all of the following characteristics: (a) a peel strength after initial compression of 10g/cm, or 20g/cm, or 30g/cm, or 40g/cm, or 50g/cm, or 60g/cm, or 70g/cm, or 80g/cm, or 90g/cm, or 100g/cm, or 110g/cm, or 120g/cm, or 130g/cm, or 140g/cm to 150g/cm, or 160g/cm, or 170g/cm, or 180g/cm, or 190g/cm, or 200g/cm, or 300g/cm, or 400g/cm, or 500 g/cm; and/or (b) a peel strength after final compression of 450g/cm, or 500g/cm, or 750g/cm, or 1000g/cm, or 1100g/cm, or 1200g/cm, or 1300g/cm, or 1400g/cm, or 1500g/cm, or 1600g/cm, or 1700g/cm, or 1800g/cm, or 1900g/cm, or 2000g/cm, or 2500g/cm, or 3000g/cm, or 3500g/cm to 4000g/cm, or 5000g/cm, or 5500g/cm, or 6000 g/cm; and/or (c) a thickness of 0.5mm, or 1.0mm to 1.5mm, or 2.0mm, or 2.5mm, or 3.0mm, or 4.0mm, or 5.0mm, or 10mm, or 20mm, or 30mm, or 40mm, or 50 mm; and/or (d) crosslinking the adhesive layer with the first layer; and/or (e) crosslinking the adhesive layer with the second layer.
An article may comprise two or more embodiments disclosed herein.
Test method
Acid number (or acid value) is measured according to ASTM D1386/7. Acid number is a measure of the amount of unreacted fatty acid present in a material. The acid number is the number of milligrams of potassium hydroxide required to neutralize the free fatty acids present in one gram of material (e.g., functionalized polybutadiene). The unit of the acid value is mg KOH/g.
The coating weight was measured by: the dried coated fabric was weighed in grams using an analytical balance and the difference between the weight of the fabric and the weight of the dried coated fabric was determined. Subsequently, the coating weight was calculated by dividing the measured weight difference by the area, and the result was in grams per square meter (g/m)2) Is reported as a unit.
Density is measured according to ASTM D792, method B. Results are in grams (g)/cubic centimeter (g/cc or g/cm)3) Is recorded in units.
The "iodine number" is the mass in grams of iodine consumed by 100 grams of KOH. Iodine number is an indication of the degree of hydrogenation and is determined (g I) according to German Einheitsmethode DGF C-V11 a (53)2/100g)。
Melt Index (MI) (I)2) Measured according to ASTM D1238, 190 ℃/2.16 kilogram (kg) weight condition, and reported as grams eluted per 10 minutes (g/10 min).
Peel strength was measured via the T-peel test as described in the examples section below.
"pour point" is the lowest temperature at which a liquid becomes semi-solid and loses its flow characteristics, or in other words, the lowest temperature at which a liquid will flow. Pour point was measured according to ASTM D97.
The ring and ball softening point was measured using a Mettler Toledo FP900 thermal system (Thermosystem) according to ASTM E28.
Differential scanning calorimetryDifferential Scanning Calorimetry (DSC) can be used to measure the melting and crystallization behavior of polymers across a wide range of temperatures. For example, provided with a refrigerated cooling system (refrigerated)A cooking system; RCS) and TA Instruments Q1000 DSC of autosampler to perform this analysis. During the test, a nitrogen purge gas flow of 50ml/min was used. Melt pressing each sample to a film at about 175 ℃; the molten sample was then allowed to air cool to room temperature (about 25 ℃). 3-10mg of a 6mm diameter specimen was removed from the cooled polymer, weighed, placed in a lightweight aluminum pan (approximately 50mg), and the crimp stopped. Analysis is then performed to determine its thermal characteristics.
The thermal behavior of the sample was determined by slowly raising and lowering the sample temperature to establish a heat flow versus temperature profile. First, the sample is rapidly heated to 180 ℃ and kept isothermal for 3 minutes in order to remove its thermal history. Subsequently, the sample was cooled to-40 ℃ at a cooling rate of 10 ℃/min and kept isothermal for 3 minutes at-40 ℃. The sample was then heated to 180 ℃ at a10 ℃/minute heating rate (this is the "second heat" ramp). The cooling and second heating profiles were recorded. The cooling curve was analyzed by setting the baseline endpoint from the start of crystallization to-20 ℃. The heating curve was analyzed by setting the baseline end point from-20 ℃ to the end of melting. The value determined is the extrapolated melting onset Tm.
The melting point Tm is determined from the DSC heating curve by: a baseline is first drawn between the start and end of the melt transfer. The tangent to the data on the low temperature side of the melting peak is then plotted. Where this line intersects the baseline is the extrapolated onset of melting (Tm). This is described in Bernhard Wunderlich, Basis of Thermal Analysis (The Basis of Thermal Analysis), Thermal Characterization of Polymeric Materials (Thermal Characterization of Polymeric Materials) 92,277-278(Edith A. Turi eds., 2 nd edition 1997).
The glass transition temperature Tg was determined from the DSC heating curve in which half of the sample had acquired the heat capacity of the liquid, as described in Bernhard Wunderlich, basis of thermal analysis, thermal characterization of polymeric materials 92,278-279(Edith A. Turi eds., 2 nd edition 1997). Baselines were drawn from below and above the glass transition region and extrapolated through the Tg region. The temperature at which the heat capacity of the sample is half way between these base lines is Tg.
Gel Permeation Chromatography (GPC)Equipped with robot-assisted delivery (Roboti)c Assistant Deliver; RAD) system for sample preparation and sample injection. The concentration detector was an infrared detector (IR-5) from Polymer Char Inc. Data collection was performed using the Polymer Char DM 100 data acquisition box. The carrier solvent was 1,2, 4-Trichlorobenzene (TCB). The system was equipped with an online solvent degassing unit from Agilent. The column compartment was operated at 150 ℃. The columns were four Mixed A LS 30cm, 20 micron columns. The solvent was 1,2, 4-Trichlorobenzene (TCB) flushed with nitrogen containing about 200ppm of 2, 6-di-tert-butyl-4-methylphenol (BHT). The flow rate was 1.0mL/min and the injection volume was 200. mu.l. The "2 mg/mL" sample concentration was prepared by dissolving the sample in N2-rinsed and preheated TCB (containing 200ppmBHT) at 160 ℃ for 2.5 hours with gentle stirring.
The GPC column set was calibrated by running 20 narrow molecular weight distribution polystyrene standards. The Molecular Weight (MW) of the standards ranged from 580g/mol to 8,400,000g/mol, and the standards were contained in six "cocktail" mixtures. Each standard mixture has at least a tenfold separation between individual molecular weights. The equivalent polypropylene molecular weight of each PS standard was calculated using the Mark-houwinkcoeffective coefficients reported for polypropylene (th.g. scholte, n.l.j.meijerine, h.m.schofelers and a.m.g. brands, journal of applied polymer science (j.appl.polymer.sci.), 29,3763-82(1984)) and the Mark-houwink coefficients reported for polystyrene (e.p.otocka, r.j.roe, n.y.hellman and p.m.mullia, & Macromolecules (Macromolecules), 4,507(1971)) using the following equation:
Polymer and method of making same
a
log K
Polypropylene
0.725
-3.721
Polystyrene
0.702
-3.900
The log molecular weight calibration was generated using a fourth order polynomial fit as a function of elution volume. The number average molecular weight (Mn) and the weight average molecular weight (Mw) were calculated according to the following equations:
Mass detector constants, laser light scattering detector constants, and viscometer detector constants were determined using standard references (the reference polymer is a linear polyethylene homopolymer) with known weight average molecular weight values (Mw 120,000 g/mol; dn/dc-0.104 mL/g; MWD 2.9) and intrinsic viscosities (1.873 dL/g). The chromatographic concentration is assumed to be low enough to eliminate the effect on the second coefficient of Virial coefficient (concentration effect on molecular weight).
The systematic method for determining detector deviation was implemented in a manner consistent with that disclosed by Balke and Mourey et al (Mourey and Balke, chapter 12 of polymer Chromatography, (1992)) (Balke, thidiratsakul, Lew, Cheung and Mourey, chapter 13 of polymer Chromatography, (1992)), using data obtained from both detectors, under simultaneous analysis of a standard reference (linear polyethylene homopolymer) and a narrow polystyrene standard with known weight average molecular weight values (Mw 120,000 g/mol; dn/dc-0.104 mL/g; MWD-2.9) and intrinsic viscosity (1.873 dL/g). The systematic approach is to optimize the individual detector biases to yield molecular weight results as close as possible to those observed using conventional GPC methods.
Some embodiments of the invention will now be described in detail in the following examples.
Examples of the invention
The materials used to manufacture the articles are provided in table 1 below.
Table 1. starting materials.
1. Preparation of adhesive composition
An ethylene-based polymer stock solution containing 10 wt% ethylene-based polymer (based on the total weight of the ethylene-based polymer stock solution) was prepared by directly dispersing the ethylene-based polymer particles in the solvent at 85 ℃ under magnetic stirring, and stirring for an additional 2 hours. A tackifier stock solution containing 20 wt% tackifier (based on the total weight of the tackifier stock solution) was prepared by dissolving the tackifier directly in a solvent at 60 ℃ under magnetic stirring. For CS 28, the solvent is solvent B. For all other examples and comparative samples, the solvent was solvent a.
The adhesive composition was prepared by mixing the ethylene-based polymer stock solution, tackifier stock solution, plasticizer, and crosslinking agent in the desired weight ratio. The adhesive composition was stirred at room temperature (23 ℃) for 10 minutes, followed by a further 10 minutes at 80 ℃ to 85 ℃ with magnetic stirring.
2. Preparation of first layer/adhesive layer article
A fabric roll containing PET fibers and cotton fibers ("PET-cotton fabric") was cut into two strips of different sizes: 15.24cm by 2.54cm and 15.24cm by 15.24cm (length by width). The adhesive composition was applied to the surface of each strip using a brush for the 15.24cm by 2.54cm strip and a casting bar for the 15.24cm by 15.24cm strip. In each case, a 12.7cm length of the strip was coated with the adhesive composition. Only one side of the PET-cotton fabric was coated. The coated PET-cotton fabric strip was dried in an oven at 80 ℃ for 5 minutes to form an adhesive layer (PET-cotton fabric/adhesive layer structure) on the PET fabric. The coating weight was measured. The process is repeated as necessary to achieve the desired coating weight. The 15.24cm by 15.24cm structure was cut into 15.24cm by 2.54cm structures. A control sample (CS 18) was prepared without the adhesive composition on PET-cotton fabric.
The coating weights of each inventive example and comparative sample adhesive layer (dry adhesive composition) applied to PET fabric are provided in tables 2 to 4. The compositions of the adhesive layers of the examples and comparative samples are provided in tables 2-4.
Article with PET-Cotton Fabric/adhesive layer/OBC layer
Applying INFUSETM9007 ethylene/1-octene multiblock copolymer ("OBC") (Density 0.866 g/cc; melt index 0.5g/10min (190 ℃/2.16 kg); melting point 119 ℃; Mw ═ C>10,000 g/mol; from dow chemical company) (46.08 wt%); n-330 carbon black (32.26 wt%); Hi-SilTM210 silica (from PPG industries, Inc.) (9.22 wt%); SR-350 adjuvant (TMPTMA, from Sartomer company) (1.38% by weight); SUNPARTM2280 Paraffin oil (from Holly frontier Refining and sales Limited liability Co., Ltd.)&Marking LLC)) (6.91 wt%); LUPEROXTMDC40P-SP2 crosslinker (dicumyl peroxide, from arkema) (2.30 wt%); AGERITETMRESIN D antioxidant (polymerized 1, 2-dihydro-2, 2, 4-trimethylquinoline from Vanderbilt Chemicals, LLC, Vanderbilt Chemicals, Vanderbilt), 0.46% by weight; VANOXTMZMTI antioxidant (2-mercaptotolylindazole zinc from van der balt chemicals llc) (0.92 wt%); and VANOXTMCDPA antioxidant (4,4' -bis (α, α -dimethylbenzyl) diphenylamine, from van der waals chemical, llc) (0.46 wt%) was weighed into an extruder and blended in the extruder to form OBC groupsA compound (I) is provided. The OBC composition was extruded and cut into 15.24cm by 2.54cm strips.
The OBC tape was contacted with the surface of the adhesive layer in the PET-cotton fabric/adhesive layer structure prepared as described above. Forming an article having the structure: PET-cotton fabric/adhesive layer/OBC layer.
4. Initial compression and adhesion test-T Peel test
Initial compressionThe PET-cotton fabric/adhesive layer/OBC layer article was preheated to 80 ° for 2 minutes and compressed twice using a 2.6kg roller. For examples 1-27 and comparative samples 2-28, the initial compression profiles were as follows: the temperature is 80 ℃; the pressure is 0.1-0.2 MPa; the time is 2-4 seconds. For examples 29-40 and comparative sample 33, the initial compression profiles were as follows: the temperature is 70 ℃; the pressure is 0.1-0.2 MPa; the time is 2-4 seconds. After initial compression, the samples were aged at 23 ℃ and 40% to 50% relative humidity for at least 5 hours.
Adhesion testA TA XT Plus Texture Analyzer from Texture Technologies Corp. was used to peel off the PET-cotton fabric and OBC layer at room temperature (23 ℃) at a speed of 5.08cm/min and a peel distance of 7.62 cm. The average peel strength (g/cm) was determined from the gram-force versus distance curve. Two or three test samples were tested and the average peel strength was reported. The adhesion between the PET-cotton fabric and the OBC layer and the respective adhesive layer located between the PET cotton fabric and the OBC layer is provided in tables 2 to 4.
5. Final compression and adhesion test-T Peel test
Final compressionAfter the initial compression tack test, the separated PET-cotton fabric/adhesive layer/OBC layer article was re-tacked at 80 ℃ following the above initial compression procedure. Subsequently, for examples 1-17 and comparative samples 2-18, a sample of the PET-cotton fabric/adhesive layer/OBC layer article was placed in an oven at 180 ℃ for 20 minutes (without pressure). Also for examples 1-17 and comparative samples 2-18, one PET-cotton fabric/adhesive layer/OBC layer article sample was preheated to 130 ℃ for 2 minutes and compressed using a compression molder with the following final compression profile: the temperature is 130 ℃; the pressure is 1.5 MPa; the time period was 2 minutes. For examples 21-25 and comparative samplesArticles 19-28, PET-cotton fabric/adhesive layer/OBC layer article samples were pre-heated to 130 ℃ for 2 minutes and compressed using a compression molder with the following final compression profile: the temperature is 130 ℃; the pressure is 1.5 MPa; the time period was 2 minutes. For examples 29-40 and comparative sample 33, PET-cotton fabric/adhesive layer/OBC layer article samples were pre-heated to 180 ℃ for 2 minutes and compressed using a compression molder with the following final compression profile: the temperature is 180 ℃; the pressure is 0.689 MPa; the time period was 2 minutes. The samples were aged at 23 ℃ and 40% to 50% relative humidity for at least 5 hours.
Adhesion testA TA XT Plus Texture Analyzer from Texture Technologies Corp. was used to peel off the PET-cotton fabric and OBC layer at room temperature (23 ℃) at a speed of 5.08cm/min and a peel distance of 20.32 cm. The average peel strength (g/cm) was determined from the gram-force versus distance curve. Two or three test samples were tested and the average peel strength was reported. The adhesion between the PET-cotton fabric and the OBC layer and the respective adhesive layer located between the PET cotton fabric and the OBC layer is provided in tables 2 to 4.
In tables 2 to 4, the adhesive layer is denoted by the letter "a" and the PET-cotton fabric/adhesive layer/OBC layer article is denoted by the letter "B". By way of explanation, the PET-cotton fabric/adhesive layer/OBC layer "1B" contains an adhesive layer "1A" -thus ex.1 constitutes "1A" and "1B".
6. Results and discussion
As shown, from (A) an adhesive layer comprising an MAH-g-ethylene/1-octene copolymer having a melt index of 0.1-300g/10min, 0.01-45 wt% MAH-g-polybutadiene, a tackifier and a crosslinker; (B) PET-cotton fabric; and (C) OBC layers (Ex.1-40) advantageously exhibit both (i) a peel strength after initial compression of greater than 10g/cm and (ii) a peel strength after final compression of greater than 450 g/cm. Thus, examples 1-40 would be suitable for use as automotive timing belts.
In contrast, the composition is prepared from (A) MAH-g-ethylene/1-octene copolymer (AFFINITY) with melt index of more than 300g/10minTMGA1000R, melt index 660g/10min), 0.01-45 wt% MAH-g-polybutadiene, a tackifier and a cross-linking agent; (B) PET-cotton fabric; and(C) the article formed with the OBC layer (CS 8) exhibited a low peel strength after initial compression of 0 g/cm. Therefore, CS 8 would not be suitable for use as an automotive timing belt.
Further, the adhesive comprises (A) an adhesive layer containing an unfunctionalized ethylene/1-octene copolymer having a melt index of 0.1 to 50g/10min, 0.01 to 45 wt% of MAH-g-polybutadiene, a tackifier and a crosslinking agent; (B) PET-cotton fabric; and (C) an OBC layer (CS 7-11) exhibits (i) low peel strength (0-8.66g/cm) after initial compression. Therefore, CS 7-11 would not be suitable for use as an automotive timing belt.
TABLE 2 adhesive layer and article◇
CS-comparative sample N/A-not applicable
◇The weight percentages are based on the total weight percentage of the adhesive layer.
TABLE 3 adhesive layer and article◇
CS-comparative sample N/A-not applicable◇The weight percentages are based on the total weight percentage of the adhesive layer.
TABLE 4 adhesive layer and article◇
CS-comparative sample◇The weight percentages are based on the total weight percentage of the adhesive layer.
It is specifically intended that the present invention not be limited to the embodiments and illustrations contained herein, but include modified forms of those embodiments including portions of the embodiments and combinations of elements of different embodiments as come within the scope of the following claims.
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